A lixiviação de elementos tóxicos presentes nas cinzas de carvão causa contaminação no meio ambiente e é, por isso, motivo de grande preocupação. Ensaios em batelada e em coluna de leito fixo foram realizados para avaliar a estabilização de As, Cr, Mo e Se em cinzas leve de carvão modificadas com orgânosilano (OS) e surfactante de amônio quaternário (SF). As cinzas leve utilizadas foram coletadas na Usina Termelétrica da Figueira, localizada na cidade de Figueira, Estado do Paraná. Nos ensaios em batelada, em primeiro lugar, avaliou-se a influência da relação massa de cinzas/volume de água na concentração dos elementos lixiviados das cinzas não tratadas. Posteriormente, determinou-se o pH, a condutividade e as capacidades de imobilização dos elementos tóxicos presentes nas cinzas após a modificação. As reduções de concentração usando OS foram de 89%, 77%, 42% e 11% para Cr, Mo, As e Se, respectivamente. Quando SF foi utilizado para o tratamento das cinzas, a redução de concentração nos lixiviados foi superior a 60% para todos os elementos. As cinzas tratadas foram caracterizadas em relação ao ponto de carga zero, morfologia, grupos funcionais, mineralogia e hidrofobicidade. As superfícies das cinzas tratadas com OS e SF apresentaram carga superficial positiva em água. A composição mineralógica e a morfologia das cinzas não foram alteradas após o tratamento, enquanto mudanças nos grupos funcionais foram observadas. Esse resultado corroborou com o observado nos testes de hidrofobicidade onde, as cinzas tratadas com OS e SF na proporção 1:10 foram classificadas como material extremamente hidrofóbico e na proporção 1:100 foram classificadas como material fortemente hidrofóbico, confirmando que foi efetivo o tratamento das cinzas com os agentes imobilizadores. Na segunda etapa do estudo foram realizados três ensaios de lixiviação em colunas contendo cinzas de carvão e solo coletado na região da Usina Termelétrica da Figueira. Nos ensaios foram usadas cinzas não tratadas, cinzas tratadas com OS e cinzas tratadas com SF nas diluições de maior efetividade selecionadas pelos ensaios em batelada. Nas colunas foi aplicado um volume de chuva ácida sintética simulando a precipitação que ocorre na região. Na coluna com cinzas tratadas com OS ocorreu redução considerável na concentração de As e principalmente do Cr. Após o tratamento com SF, as concentrações de As e Cr reduziram aproximadamente 30%. Em ambos os tratamentos, as concentrações de Mo e Se também foram reduzidas. Os resultados evidenciaram que tanto o orgânosilano, quanto o surfactante podem ser utilizados como agentes imobilizadores para a retenção de elementos tóxicos presentes em cinzas de carvão. / The leaching of toxic elements in coal ash causes contamination of the environment and is therefore of great concern. Batch and column tests were performed to evaluate the stabilization of As, Cr, Mo and Se in fly ash modified with organosilane (OS) and quaternary ammonium surfactant (SF). The fly ashes used were collected at the Figueira Thermoelectric Plant, located in the city of Figueira, State of Paraná. In the batch tests, first, the influence of ash / volume ratio on the concentration of the leached elements of the untreated ash was evaluated. Subsequently, the pH, conductivity and immobilization capacities of the toxic elements present in the ashes after the modification were determined. The reductions in the concentrations of toxic elements using OS were 89%, 77%, 42% and 11% for Cr, Mo, As and Se, respectively. When SF was used for ash treatment, the concentration reduction in the leachates was greater than 60% for all elements. The treated ash was characterized in relation to zero charge point, morphology, functional groups, mineralogy and hydrophobicity. OS and SF treated ash surfaces showed a positive surface charge in water. The mineral composition an morphology of the ashes was not altered after treatment, while changes in the functional groups were observed. This result corroborated with that observed in the hydrophobicity tests, where ashes treated with OS and SF in the proportion 1:10 were classified as extremely hydrophobic material and in the proportion 1: 100 were classified as strongly hydrophobic material, confirming that the treatment of the ashes with immobilizing agents were efficient. In the second stage of the study three leaching tests were carried out on columns containing coal ash and soil collected in the Figueira Thermoelectric Power Plant region. In the tests, untreated fly ash, OS treated fly ash and SF treated fly ash were used at the most effective dilutions selected by batch tests. In the columns a synthetic acid rain was applied simulating the precipitation that occurs in the region. In the column with ash treated with OS there was a considerable reduction in the concentration of As and especially of Cr. After treatment with SF, concentrations of As and Cr reduced approximately 30%. In both treatments, the concentrations of Mo and Se were also reduced. The results showed that both the organosilane and the surfactant can be used as immobilizers for the retention of toxic elements present in coal ash.

[pt] O surfactante pulmonar é um sistema lipo-proteico que atua na interface alveolar com vital importância para manter funcional a mecânica respiratória. Os comprometimentos na sua função estão associados a diversas infecções pulmonares. Os sistemas de administração de fármacos baseados em surfactantes pulmonares derivados de animais são complexos, dificultando a compreensão do papel individual das moléculas hóspedes nas suas interações com a membrana. Aqui apresentamos uma caracterização de um extrato surfactante de pulmão porcino de grau clínico misturado com os antibióticos Levofloxacina e Claritromicina, usando uma abordagem multi-técnica – em conjunto com a metodologia de monocamadas de Langmuir– consistindo de isotermas de pressão de superfície-area, microscopia de ângulo de Brewster (BAM), espectroscopia de reflexão-absorção do infravermelho com modulação da polarização (PM-IRRAS), reflectometria de nêutrons (NR), ensaios in vitro e simulações de dinâmica molecular. Avaliou-se o efeito de ambos os antibióticos na estrutura das monocamadas de surfactantes de origem porcino bem como em monocamadas de DPPC. Foi revelado que a estabilidade / integridade das monocamadas é preservada na presença de ambas as drogas. Os sistemas mistos de antibiótico / surfactante pulmonar aumentam a atividade antibacteriana contra bactérias Gram-positivas (Bacillus cereus) e Gram-negativas (Escherichia coli). Essas descobertas fornecem novas percepções sobre a otimização de sistemas eficientes de administração de medicamentos para o tratamento de condições patológicas no nível respiratório. / [en] The lipo-proteic surfactant system acting at the alveolar interface is of vital importance for keeping functional the respiratory mechanics. Its impairments are associated with several pulmonary infections. Drug delivery systems based on animal-derived lung surfactants are complex making it difficult to understand the individual role of guest molecules in membrane interactions. Here we present a characterization of a clinical-grade porcine lung surfactant extract mixed with the antibiotics Levofloxacin and Clarithromycin, using a multi-technique approach –in conjunction with the Langmuir-monolayer methodology– consisting of surface pressure-area isotherms, Brewster angle microscopy (BAM), polarization modulation-infrared reflection-adsorption spectroscopy (PM-IRRAS), neutron reflectometry (NR), in vitro assays, and molecular dynamics simulations. The effect of both antibiotics in the structure of porcine lung surfactant monolayers as well as in DPPC monolayers was examined. It was revealed that the stability/integrity of the monolayers is preserved in the presence of both drugs. The mixed antibiotic/lung surfactant systems enhance the antibacterial activity against Gram-positive (Bacillus cereus) and Gram-negative (Escherichia coli) bacteria. These findings provide new insights into the optimization of efficient drug delivery systems for the treatment of pathological conditions at the respiratory level.

The widespread environmental occurrence of chemical pollutants presents an ongoing threat to human and ecosystem health. This challenge is compounded by the diversity of chemicals used in industry, commerce, agriculture and medicine, which results in a spectrum of potential fates and exposure profiles upon their inevitable release into the environment. This, in turn, confounds risk assessment, where challenges persist in accurate determination of concentrations levels, as well as spatial and temporal distributions, of pollutants in environmental media (e.g., water, air, soil and sediments). Passive sampling technologies continue to gain acceptance as a means for simplifying environmental occurrence studies and, ultimately, improving the quality of chemical risk assessment. Passive samplers rely on the accumulation of a target analyte into a matrix via molecular diffusion, which is driven by the difference in chemical potential between the analyte in the environment and the sampling media (e.g., sorbent phase). After deployment, the target analyte can be extracted from the sampling media and quantified, providing an integrated, time-weighted average pollutant concentration via a cost-effective platform that requires little energy or manpower when compared to active (e.g., grab) sampling approaches. While a promising, maturing technology, however, limitations exist in current commercially available passive samplers; they are typically limited in the types of chemicals that can be targeted effectively, can require long deployment times to accumulate sufficient chemical for analysis, and struggle with charged analytes. In this dissertation, we have designed a next-generation, nanofiber sorbent as a passive sampling device for routine monitoring of both legacy and emerging organic pollutant classes in water and sediment. The polymer nanofiber networks fabricated herein exhibit a high surface area to volume ratio (SA/V values) which shortens the deployment time. Uptake studies of these polymer nanofiber samplers suggest that field deployment could be shortened to less than one day for surface water analysis, effectively operating as an equilibrium passives sampling device, and twenty days for pore water analysis in soil and sediment studies. By comparison, most commercially available passive sampler models generally require at least a month of deployment before comparable analyses may be made. Another highlight of the nanofiber materials produced herein is their broad target application range. We demonstrate that both hydrophobic (e.g., persistent organic pollutants, or POPs, like PCBs and dioxin) and hydrophilic (e.g., emerging pollutant classes including pesticides, pharmaceuticals and personal care products) targets can be rapidly accumulated with our optimal nanofibers formulations. This suggests that one of our devices could potentially replace multiple commercial passive sampling devices, which often exhibit a more limited range of analyte targets. We also present several approaches for tailoring nanofiber physical and chemical properties to specifically target particular high priority pollutant classes (e.g., PFAS). Three promising modification approaches validated herein include: (i) fabricating carbon nanotube-polymer composites to capture polar compounds; (ii) introducing surface-segregating cationic surfactants to target anionic pollutants (e.g., the pesticide 2,4-D and perfluorooctanoic acid or PFOA); and (iii) use of leachable surfactants as porogens to increase nanofiber pore volume and surface area to increase material capacity. Collectively, outcomes of this work will guide the future development of next generation passive samplers by establishing broadly generalizable structure-activity relationships. All told, we present data related to the influence on the rate and extent of pollutant uptake in polymer nanofiber matrices as a function of both physical (specific surface area, pore volume, and diameter) and chemical (e.g., bulk and surface composition, nanofiber wettability, surface charge) nanofiber properties. We also present modeling results describing sampler operation that can be used to assess and predict passive sampler performance prior to field deployment. The electrospun nanofiber mats (ENMs) developed as passive sampling devices herein provide greater functionality and allow for customizable products for application to a wide range of chemical diverse organic pollutants. Combined with advances in and expansion of the nanotechnology sector, we envision this product could be made commercially available so as to expand the use and improve the performance of passive sampling technologies in environmental monitoring studies.

Films of phospholipids and biologically relevant surfactants at the air-water interface provide a well-defined medium to study molecular alignment, phase behavior and interactions of biomembranes and lung surfactant with exogenous materials. Interactions between lung surfactant interfaces and solid particles are of particular interest due to the increased use of nanomaterials in industrial applications and the promise of polymeric particles in pulmonary drug delivery. Understanding such interactions is necessary to avoid potential adverse effects on surfactant function after exposure to particles. In this thesis, the mechanisms of surfactant inhibition after exposure to submicron particles via different routes were investigated. The effects of carboxyl-modified polystyrene particles (200 nm) on films of dipalmitoyl phosphatidylcholine (DPPC) and Infasurf (calf lung surfactant extract) were studied. Surfactants were exposed to different concentrations of particles in a Langmuir trough with symmetric surface compression and expansion. Surface tension, potential, microstructure and topology were examined to monitor particle effects on surfactant function. Several methods of surfactant exposure to particles were studied: particle injection into the subphase after spreading surfactant monolayers (subphase injection), mixing the particles with the subphase and spreading the surfactant on top (monolayer addition) and particle aerosolization onto surfactant films. Studies with DPPC monolayers revealed that particle-surfactant interactions are dependent on the particle introduction method. In the subphase injection method, particles did not penetrate the monolayer and no inhibitory effects on surfactant function were observed. However, in the monolayer addition method, particles caused a premature monolayer collapse and hindered surfactant respreading likely by penetrating into the DPPC monolayer. Finally, particle aerosolization on surfactant was performed to mimic the physiologically relevant route of surfactant exposure to particles. Particle aerosolization on DPPC monolayers significantly inhibited surfactant function in the lung-relevant surface tension range. When aerosolized on Infasurf, particles caused inhibitory effects as a function of time suggesting adsorption of surfactant components on particle surfaces as the main mechanism of interaction. This research will enhance understanding of the mechanisms of particle-induced surfactant dysfunction, thereby providing information for the safe design of polymeric particles for drug delivery and for developing guidelines for particles used in occupational settings.

acase@tulane.edu

The nasal mucosa provides a rapid, noninvasive route for drug administration to the systemic circulation and even potentially to the CNS. Nanoparticles made from the biodegradable polymer, PLGA, are of great interest for use in drug delivery systems due to PLGA’s relative safety and ease of surface modification. Nanoparticles may provide improved targeting and transport through the nasal mucosa. However, the optimal nanoparticle sizes and surface properties for intranasal delivery are unknown. In this study, we prepared PLGA nanoparticles within a size range of 50-70 nm containing the lipophilic fluorescent dye, Nile Red, using a surfactant-free nanoprecipitation method. The resulting nanoparticles were evaluated using dynamic light scattering and scanning electron microscopy. Nanoparticle uptake into the nasal mucosa was determined by exposing the tissues to nanoparticle dispersions for 30 or 60 minutes. The in vitro uptake of the nanoparticles by the nasal mucosal tissues revealed that the Nile Red-loaded PLGA nanoparticles were transported across the epithelial layer and accumulated in the sub-mucosal connective tissues. Nanoparticle uptake in the full thickness tissues was time dependent where 2% of the total loads of nanoparticles exposed to the tissues were measured in the mucosal tissue after 30 minutes and 4% were present in the tissues after 60 minutes. The rapid and measurable transfer of PLGA nanoparticles into the nasal mucosal tissues indicate that they may be an efficient delivery vehicle for drugs with either local or systemic activities.

Recently designed Pepfactants® are an innovative type of nano-technological products, which could potentially replace conventional surfactants in broad-ranging applications. Currently, Pepfactants® technology is still in an initial design period at the laboratory scale. In order to develop the industrial-scale production of Pepfactants®, the design group has proposed simulated strategies for industrial-scale Pepfactants® manufacture and a desire to improve these strategies with regards to sustainability. This project aimed to assist Pepfactants® designers to understand the environmental footprint of simulated Pepfactant® AM1 manufacturing process, using the methodology of Life Cycle Assessment (LCA) – a comprehensive tool to quantify the environmental impacts from products and processes. To find the environmental shortcomings of the proposed manufacturing process for Pepfactant® AM1, the LCA outcomes were compared with published life cycle information of traditional chemical surfactant Lineal Alkylbenzene Sulphonate (LAS) production. Following LCA methodology, a life cycle inventory was compiled based on the simulated AM1 manufacture, which determined the environmental impact assessment for both AM1 and LAS production. In the LCA boundaries disregarding the usage of both surfactants, the quantitative LCA comparison results indicated that raw material and energy requirements of AM1 manufacture were much higher than LAS production, estimated to be 3,186 t/t AM1 against 31.1t/t LAS and 1,564,000MJ/t AM1 against 69,870MJ/t LAS respectively. Additionally, compared with LAS production, enormous water consumption (2,651 t/t AM1) and CO2 emission (522 t/t AM1) were also shown to be severe environmental problems for AM1 manufacture. Furthermore, the AM1 manufacture presents apparent problems with environmental impacts of nutrification, human toxicity, photochemical oxidant formation and acidification in comparison with LAS production. Other than providing the optimisation point in the view of environmental impacts for Pepfactant® AM1 manufacture, the results of experimental work in this project showed that as the surfactant concentration increases a greater foam height of Pepfactant® AM1 was achieved than when (from 7mm to 52mm between 15μM and 100μM) compared with LAS (from 8mm to 53mm between 31.3μM and 2,000μM) in the same aeration duration. This result demonstrated the great potential of AM1 to replace LAS based on the LCA functional unit – 1 tonne of products. The experiments results implied that 1 tonne of AM1 is able to have the same foaming ability as approximate 25 tonnes of LAS. Consequently, the environmental impacts from Pepfactant® AM1 manufacture are reduced by 25 times in the extended LCA boundaries linked to the quantitative usage comparison of these two surfactants. / http://proxy.library.adelaide.edu.au/login?url= http://library.adelaide.edu.au/cgi-bin/Pwebrecon.cgi?BBID=1317664 / Thesis (M.Eng.Sc.) -- University of Adelaide, School of Chemical Engineering, 2008

<p>The use of catanionic drug-surfactant mixtures was proven to be an efficient novel method of obtaining prolonged drug release from gels. It was shown that various commonly used drug compounds are able to form catanionic mixtures together with oppositely charged surfactants. These mixtures exhibited interesting phase behaviour, where, among other structures, vesicles and large worm-like or branched micelles were found. The size of these aggregates makes them a potential means of prolonging the drug release from gels, as only monomer drugs in equilibrium with larger aggregates were readily able to diffuse through the gel. When the diffusion coefficient for drug release from the formulation based upon a catanionic mixture was compared to that obtained for the drug substance and gel alone, the coefficient was some 10 to 100 times smaller.</p><p>The effects of changes in the pH and ionic strength on the catanionic aggregates was also investigated, and this method of prolonging the release was found to be quite resilient to variations in both. Although the phase behaviour was somewhat affected, large micelles and vesicles were still readily found. The drug release was significantly prolonged even under physiological conditions, that is, at a pH of 7.4 and an osmolality corresponding to 0.9% NaCl.</p><p>Surfactants of low irritancy, capric and lauric acid, may successfully be used instead of the more traditional surfactants, such as sodium lauryl sulfate (SDS), and prolonged release can still be obtained with ease.</p><p>Some attempts to deduce the release mechanism from the proposed systems have also been made using transient current measurements, dielectric spectroscopy, and modelling of the release using the regular solution theory. In these studies, the previous assumptions made concerning the mechanism responsible for the release were confirmed to a large extent. Only small amounts of the drug existed in monomer form, and most seemed to form large catanionic aggregates with the oppositely charged surfactant.</p>

Nonionic surfactants are commonly used to stabilize proteins during upstream and downstream processing and drug formulation. Surfactants stabilize the proteins through two major mechanisms: (i) their preferential location at nearby interfaces, in this way precluding protein adsorption; and/or (ii) their association with protein into "complexes" that prevent proteins from interacting with surfaces as well as each other. In general, both mechanisms must be at play for effective protein stabilization against aggregation and activity loss, but selection of surfactants for protein stabilization currently is not made with benefit of any quantitative, predictive information to ensure that this requirement is met. In certain circumstances the kinetics of surface tension depression (by surfactant) in protein-surfactant mixtures has been observed to be greater than that recorded for surfactant alone at the same concentration. We compared surface tension depression by poloxamer 188 (Pluronic�� F68), polysorbate 80 (PS 80), and polysorbate 20 (PS 20) in the presence and absence of lysozyme and recombinant protein, at different surfactant concentrations and temperatures. The kinetic results were interpreted with reference to a mechanism for surfactant adsorption governed by the formation of a rate-limiting structural intermediate (i.e., an "activated complex") comprised of surfactant aggregates and protein. The presence of lysozyme was seen to increase the rate of surfactant adsorption in relation to surfactant acting alone at the same concentrations for the polysorbates while less of an effect was seen for Pluronic�� F68. However, the addition of salt was observed to accelerate the surface tension depression of Pluronic�� F68 in the presence of lysozyme. The addition of a more hydrophobic, surface active protein (Amgen recombinant protein) in place of lysozyme resulted in greater enhancement of surfactant adsorption than that recorded in the presence of lysozyme. A simple thermodynamic analysis indicated the presence of protein caused a reduction in ���G for the surfactant adsorption process, with this reduction deriving entirely from a reduction in ���H. We suggest that protein accelerates the adsorption of these surfactants by disrupting their self associations, increasing the concentration of surfactant monomers near the interface. Based on these air-water tensiometry results, it is fair to expect that accelerated surfactant adsorption in the presence of protein (observed with PS 20 and PS 80) will occur with surfactants that stabilize protein mainly by their own adsorption at interfaces, and that the absence of accelerated surfactant adsorption (observed with F68) will be observed with surfactants that form stable surfactant-protein associations. Optical waveguide lightmode spectroscopy was used to test this expectation. Adsorption kinetics were recorded for surfactants (PS 20, PS 80, or F68) and protein (lysozyme or Amgen recombinant protein) at a hydrophilic solid (SiO���-TiO���) surface. Experiments were performed in sequential and competitive adsorption modes, enabling the adsorption kinetic patterns to be interpreted in a fashion revealing the dominant mode of surfactant-mediated stabilization of protein in each case. Kinetic results confirmed predictions based on our earlier quantitative analysis of protein effects on surface tension depression by surfactants. In particular, PS 20 and PS 80 are able to inhibit protein adsorption only by their preferential location at the interface, and not by formation of less surface active, protein-surfactant complexes. On the other hand, F68 is able to inhibit protein adsorption by formation of protein-surfactant complexes, and not by its preferential location at the interface. / Graduation date: 2013 / Access restricted to the OSU Community at author's request from Sept. 24, 2012 - Feb. 24, 2013.

A suitable management of the pharmaceutical property is needed and helpful to design a desired nanoparticulate delivery system, which includes the carrier nature, particle size and size distribution, morphology, surfactant stabiliser according to the technique applied, drug-loading ratio and encapsulation efficiency, surface property, etc. All will influence the in vitro release, in vivo behaviour and tissue distribution of administered particulate drug loaded nanoparticles. The main purpose of the present work was to determine the effect of drug loading ratio when employing TPGS as surfactant stabiliser and/or matrix material to improve the nanoparticulate formulation. The model drug employed was paclitaxel. / Singapore-MIT Alliance (SMA)